Реакция #67471

Уравнение реакции

2-(2-Bromo-4-nitrophenyl)-2-methylpropane-1,3-diol

Cyanomethylenetributylphosphorane

Tin(II) chloride dihydrate

→

3-bromo-4-(3-methyloxetan-3-yl)aniline

Выход 32.0%

Растворители

benzene

Условия реакции

Обработка

1. 1
   ДругоеThe mixture was evaporated to dryness
2. 2
   workup.DISSOLUTIONre-dissolved in 4 mL of EtOH
3. 3
   Температураthe resulting solution was heated at 70° C. for 1 hour
4. 4
   ТемператураThe mixture was cooled to room temperature
5. 5
   Другоеquenched with a saturated aqueous solution of sodium bicarbonate
6. 6
   ЭкстракцияThe mixture was then extracted three times with ethyl acetate
7. 7
   ДругоеThe combined ethyl acetate extracts were evaporated to dryness
8. 8
   Другоеpurified by preparative LC/MS

Методика

2-(2-Bromo-4-nitrophenyl)-2-methylpropane-1,3-diol (0.145 g, 0.500 mmol) was dissolved in 2.5 mL of anhydrous benzene. Cyanomethylenetributylphosphorane (CMBP) (0.181 g, 0.750 mmol) was then added and the solution was allowed to stir at room temperature for 72 hours. The mixture was evaporated to dryness and then re-dissolved in 4 mL of EtOH. Tin(II) chloride dihydrate (0.564 g, 2.50 mmol) was then added and the resulting solution was heated at 70° C. for 1 hour. The mixture was cooled to room temperature and then quenched with a saturated aqueous solution of sodium bicarbonate. The mixture was then extracted three times with ethyl acetate. The combined ethyl acetate extracts were evaporated to dryness and purified by preparative LC/MS to yield 3-bromo-4-(3-methyloxetan-3-yl)aniline as a pale yellow oil (0.032 g, 32%) NMR (400 MHz, CD3CN) δ 7.13 (dd, J=0.7, 1.8 Hz, 1H), 6.94-6.88 (m, 2H), 6.75 (br s, 2H), 4.98 (d, J=5.6 Hz, 2H), 4.51 (d, J=6.1 Hz, 2H), 1.74 (s, 3H). ESI-MS m/z calc. 241.0, found; 242.1 (M+1)+ Retention time 0.53 minutes.

Источник